CN115003775B - Colorant for heat transfer fluid and composition containing same - Google Patents

Colorant for heat transfer fluid and composition containing same Download PDF

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CN115003775B
CN115003775B CN202080076220.6A CN202080076220A CN115003775B CN 115003775 B CN115003775 B CN 115003775B CN 202080076220 A CN202080076220 A CN 202080076220A CN 115003775 B CN115003775 B CN 115003775B
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antifreeze composition
weight percent
present
colorant
antifreeze
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CN115003775A (en
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朴载润
朴贤镇
李洪基
金慈源
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Kd Fine Chemicals Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/025—Silicon compounds without C-silicon linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/063—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide having oxygen or sulfur atom(s) linked directly to the skeleton
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/108—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a phthalocyanine dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
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Abstract

The present invention relates to a colorant for a heat transfer fluid and a composition comprising the same.

Description

Colorant for heat transfer fluid and composition containing same
Technical Field
The present patent application claims priority from korean patent application No. 10-2019-0139760, which was filed on the date of 2019, 11, 4, the disclosure of which is incorporated herein by reference.
The present invention relates to a colorant for a heat transfer fluid and a composition comprising the same.
Background
A fuel cell is a cell that generates electric energy by an electrochemical reaction in which hydrogen anions generated in a cathode oxidation reaction are reduced to water at an anode, and in order to obtain high power, the fuel cell is mainly composed of a stack of cells (cells) connected in series, but a part of energy is converted into heat energy instead of electric energy due to a small amount of resistance existing inside the cells, thereby generating a large amount of heat.
Therefore, in order for the fuel cell to achieve a desired current density level without decomposing the fuel cell components, it is necessary to control the heat of the exothermic reaction generated during the electrochemical reaction, and therefore, an effective cooling system is necessary for the operation of the cell.
The use of Deionized Water (DI-Water) as early stage fuel cell system cooling Water has high electrical resistance and excellent electrical insulation and cooling performance, but has the disadvantage of freezing at a temperature of 0 ℃ or less, and is easily contaminated by ionic substances in the fuel cell system, and has a problem of rapid decrease in electrical thermal properties.
Therefore, in order to prevent freezing, substances such as calcium chloride, magnesium chloride, ethylene glycol and the like are mixed with deionized water to raise the boiling point of water and lower the freezing point. Such mixed solutions are known as antifreeze solutions, and generally include colorants to facilitate visual concentration and prevent confusion with water in industrial sites. Acid dyes, direct dyes and the like are mainly used in the fuel cell antifreeze, but the acid dyes and the direct dyes have the defects of low color rendering property and slightly low electrochemical stability.
On the other hand, the operating voltage of the fuel cell stack to which a plurality of fuel cells are connected is very high. Thus, the antifreeze is typically given a very low conductivity to prevent and minimize the risk of electric shock, current diversion and reduction in system efficiency.
However, since dyes and colorants used in existing fuel cell coolants are generally of the high conductivity ionic type, they are unsuitable for use as antifreeze for fuel cells requiring low conductivity.
Accordingly, there is a need for further research and development of novel antifreeze solutions that are electrochemically stable and have low conductivity.
Disclosure of Invention
Technical problem
The object of the present invention is to provide a colorant for a heat transfer fluid which is physically and chemically stable and exhibits excellent color strength.
Another object of the present invention is to provide an antifreeze composition comprising the above colorant.
Technical proposal
The present invention relates to a colorant for a heat transfer fluid and a composition comprising the same.
Hereinafter, the present invention will be described in more detail.
An example of the present invention relates to a colorant for a heat transfer fluid having the structure of the following chemical formula 1.
Chemical formula 1:
in the present invention, the M may be a metal or a metalloid.
In the present invention, the metal or metalloid may be boron (B), silicon (Si), aluminum (Al), gallium (Ga), indium (In), or titanium (Ti), for example, but is not limited thereto.
Silicon and boron are metalloid elements and are generally nonmetallic, but silicon and boron in the present invention refer to metallic silicon having the same crystal structure as metallic crystals and exhibiting properties close to those of metals.
In the present invention, the above L may be- (CH) 2 )m-、-COO-、-CO-、-MH-、-SO 2 -or-SO 2 NH-, but is not limited thereto.
In the present invention, m may be an integer such as an integer greater than or equal to 0, preferably an integer of 0 to 3, but is not limited thereto. Due to CH 2 It may also be absent (in this case, m=0) as a linking group, and if m > 3, the alkyl group becomes too long, resulting in a drastic decrease in the solubility of the dye in the antifreeze (water-solubility), and thus unsuitable for use as a colorant.
In the present invention, X may be any one of hydrophilic polymers such as polyethylene glycol (polyethylene glycol), polyvinyl alcohol (polyvinyl alcohol), polyvinylpyrrolidone (Polyvinylpyrrolidone) or a copolymer of two or more thereof, but is not limited thereto.
In the present invention, the above n may be an integer greater than or equal to 1, such as 1 or 2, but is not limited thereto, and the number of ligands may be 1 or 2 according to the kind of M.
In the present invention, the number average molecular weight of the hydrophilic polymer may be 150 to 20000, 200 to 20000, 250 to 20000, 300 to 20000, 350 to 20000, 150 to 15000, 200 to 15000, 250 to 15000, 300 to 15000, 350 to 15000, 150 to 10000, 200 to 10000, 250 to 10000, 300 to 10000, 350 to 10000, 150 to 5000, 200 to 5000, 250 to 5000, 300 to 5000, 350 to 5000, 150 to 3000, 200 to 3000, 250 to 3000, 300 to 3000, 350 to 3000, 150 to 1000, 200 to 1000, 250 to 1000, 300 to 1000, 350 to 1000, 150 to 500, 200 to 500, 250 to 500, 300 to 500, 350 to 500, for example, 400. When the molecular weight of the hydrophilic polymer is less than 150, the length of the polymer chain is too short, and the solubility and compatibility of the solvent in the antifreeze solution are limited; when the molecular weight of the hydrophilic polymer is more than 20000, the length of the polymer chain is too long, which hinders the condensation reaction in the synthesis process of the colorant to decrease the reaction yield, and the color development strength is also greatly reduced.
In the present invention, each of Ra to Rp may be independently hydrogen, halogen, carboxyl, sulfonic acid group, amide group, ester group, acetyl, siloxane group, C 1 To C 10 Alkyl, C 1 To C 10 Alkylene, C 1 To C 10 Alkoxy, C 1 To C 10 Oxyalkylene group, C 1 To C 10 Fluorinated alkyl, C 4 To C 20 Aralkyl groups or derivatives thereof.
In the present invention, the Ra to Rp may be substituted on 4 or 8 of the outer peripheral portions of the structure shown in the above chemical formula 1 to form a symmetrical structure or substituted on some selective portions of the outer periphery to form an asymmetrical structure.
In the present invention, the structure shown in the above chemical formula 1 may include an unsaturated bond so that pi electrons may function as a chromophore (chromophone) that absorbs energy to float and develop color, and a peripheral substituent may be bonded to the chromophore to function as an auxochrome (auxochrome) that changes the color tone of an organic compound.
In the present invention, the colorant having the structure of the above chemical formula 1 may exhibit a red-based color, and may exhibit a color change according to the kind of the substituent at the peripheral portion and the number of the substituents.
As one embodiment of the present invention, when R2, R6 and R10 in the above chemical formula 1 are fluorinated alkyl-C 6 F 13 And all other peripheral substituents are hydrogen, the above chemical formula 1 has the structure of the following chemical formula 1-1 and exhibits pink color.
Chemical formula 1-1:
another example of the present invention relates to a colorant for a heat transfer fluid having the structure of the following chemical formula 2.
Chemical formula 2:
in the present invention, the M may be a metal or a metalloid.
In the present invention, the metal or metalloid may be silicon (Si), aluminum (Al), gallium (Ga), indium (In), titanium (Ti), tin (Sn), or ruthenium (Ru), for example, but is not limited thereto.
Silicon is a metalloid element and is usually non-metal, but silicon in the present invention refers to metallic silicon having the same crystal structure as a metal crystal and exhibiting properties close to those of metal.
In the present invention, the above L may be- (CH) 2 )m-、-COO-、-CO-、-MH-、-SO 2 -or-SO 2 NH-, but is not limited thereto.
In the present invention, m may be an integer such as an integer greater than or equal to 0, preferably an integer of 0 to 3, but is not limited thereto. Due to CH 2 Acting as a linking group and may therefore be absent (where m=0), if m > 3, the alkyl group becomes too long, resulting in dye addition to the antifreeze (water-solubleSex) and thus is unsuitable for use as a colorant. In the present invention, X may be any one of hydrophilic polymers such as polyethylene glycol (polyethylene glycol), polyvinyl alcohol (polyvinyl alcohol), polyvinylpyrrolidone (Polyvinylpyrrolidone) or a copolymer of two or more thereof, but is not limited thereto.
In the present invention, the above n may be an integer greater than or equal to 1, such as 1 or 2, but is not limited thereto, and the number of ligands may be 1 or 2 according to the kind of M.
In the present invention, the number average molecular weight of the hydrophilic polymer may be 150 to 20000, 200 to 20000, 250 to 20000, 300 to 20000, 350 to 20000, 150 to 15000, 200 to 15000, 250 to 15000, 300 to 15000, 350 to 15000, 150 to 10000, 200 to 10000, 250 to 10000, 300 to 10000, 350 to 10000, 150 to 5000, 200 to 5000, 250 to 5000, 300 to 5000, 350 to 5000, 150 to 3000, 200 to 3000, 250 to 3000, 300 to 3000, 350 to 3000, 150 to 1000, 200 to 1000, 250 to 1000, 300 to 1000, 350 to 1000, 150 to 500, 200 to 500, 250 to 500, 300 to 500, 350 to 500, for example, may be 400. When the molecular weight of the hydrophilic polymer is less than 150, the length of the polymer chain is too short, and the solubility and compatibility of the solvent in the antifreeze solution are limited; when the molecular weight of the hydrophilic polymer is more than 20000, the length of the polymer chain is too long, which hinders the condensation reaction in the synthesis process of the colorant to decrease the reaction yield, and the color development strength is also greatly reduced.
In the present invention, each of Ra to Rp may be independently hydrogen, halogen, carboxyl, sulfonic acid group, amide group, ester group, acetyl, siloxane group, C 1 To C 10 Alkyl, C 1 To C 10 Alkylene, C 1 To C 10 Alkoxy, C 1 To C 10 Oxyalkylene group, C 1 To C 10 Fluorinated alkyl, C 4 To C 20 Aralkyl groups or derivatives thereof.
In the present invention, the Ra to Rp may be substituted on 4 or 8 of the outer peripheral portions of the structure shown in the chemical formula 2 to form a symmetrical structure or substituted on some selective portions of the outer periphery to form an asymmetrical structure.
In the present invention, the structure shown in the above chemical formula 2 may include an unsaturated bond so that pi electrons may function as a chromophore (chromophone) that absorbs energy to float and develop color, and a peripheral substituent may be bonded to the chromophore to function as an auxochrome (auxochrome) that changes the color tone of an organic compound.
In the present invention, the colorant having the structure of the above chemical formula 2 may exhibit a blue-to-blue-green color, and may be changed in color according to the kind of the substituent at the peripheral portion and the number of the substituents.
As an embodiment of the present invention, when Rb, rf, rj and Rn in the above chemical formula 2 are t-butyl (-tert-butyl) and all other peripheral substituents are hydrogen, the above chemical formula 2 has the structure of the following chemical formula 2-1 and exhibits a bluish green color.
Chemical formula 2-1:
as another embodiment of the present invention, when M in the above chemical formula 2 is substituted with two silicon (Si) and all other peripheral portion substituents are hydrogen, the above chemical formula 2 has the structure of the following chemical formula 2-2 and exhibits blue color.
Chemical formula 2-2:
xa and Xb of the above chemical formula 2-2 may each independently be any one of hydrophilic polymers such as polyethylene glycol (polyethylene glycol), polyvinyl alcohol (polyvinyl alcohol), polyvinylpyrrolidone (Polyvinylpyrrosidone) or a copolymer of two or more thereof, but are not limited thereto.
As another embodiment of the present invention, when the peripheral substituent of the above chemical formula 2 is triethylene glycol (TEG), the above chemical formula 2 has a structure of the following chemical formulas 2 to 3 and exhibits bluish green.
Chemical formula 2-3:
the colorant of the present invention has been described above by way of specific examples, but the present invention is not limited thereto, and the colorant of the present invention having various structures and physical properties can be synthesized by first synthesizing phthalonitrile derivatives as starting materials and then adjusting the component ratios thereof.
The colorant of the present invention has a structure in which the hydrophilic polymer is substituted at the molecular axis center (aixal), and therefore is excellent in chemical stability and thermal stability, and particularly has high affinity with the components constituting the antifreeze composition, and therefore is excellent in solubility in the antifreeze.
The colorant of the present invention has thermal stability in a temperature range of 250 ℃ or less, and the weight loss ratio may be 10% or less.
In the invention, the solubility of the colorant in the antifreeze composition can reach more than 1.0 g/L. The solubility in the above range can sufficiently exhibit color development.
In the present invention, the above-mentioned antifreeze composition may be a glycol-based antifreeze composition, such as an ethylene glycol-based antifreeze composition, but is not limited thereto.
The colorant of the present invention is excellent in solubility in the antifreeze composition, and therefore can be well mixed in the antifreeze composition. Further, it is excellent in not only physical and chemical stability but also color development in particular, and even a small amount can exhibit excellent color characteristics in the antifreeze composition. Therefore, the colorant of the present invention is particularly suitable for use as a colorant of an antifreeze composition and can exhibit excellent characteristics.
Further, since the colorant of the present invention has excellent electrical insulation properties, the antifreeze composition containing the colorant of the present invention has advantages of extremely low electrical conductivity and extremely low contamination of the ion exchange resin by the fuel cell when used in the fuel cell.
Another example of the present invention relates to an antifreeze composition comprising a colorant, a glycol compound, and water.
In the present invention, the above-mentioned colorant may be a colorant having the structure of the following chemical formula 1 and/or a colorant having the structure of chemical formula 2.
Chemical formula 1:
chemical formula 2:
the descriptions of chemical formula 1 and chemical formula 2 are as described above.
In the present invention, the colorant having the structure of chemical formula 1 and/or the colorant having the structure of chemical formula 2 may be contained in the above-described antifreeze composition in an amount of 0.001 to 10.000 weight percent, 0.001 to 9.000 weight percent, 0.001 to 8.000 weight percent, 0.001 to 7.000 weight percent, 0.001 to 6.000 weight percent, 0.001 to 5.000 weight percent, 0.001 to 4.000 weight percent, 0.001 to 3.000 weight percent, 0.001 to 2.000 weight percent, 0.001 to 1.000 weight percent, 0.001 to 0.100 weight percent, 0.001 to 0.000 weight percent, for example, 0.002 to 0.008 weight percent, based on the total weight of the antifreeze composition.
In the present invention, the above glycol compound may use any one known in the art, for example, at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, polyalkylene glycol, and glycol ether, and may be ethylene glycol, for example, but not limited thereto.
In the present invention, the content of the above glycol compound may be 30 to 70 weight percent, 30 to 65 weight percent, 30 to 60 weight percent, 30 to 55 weight percent, 35 to 70 weight percent, 35 to 65 weight percent, 35 to 60 weight percent, 35 to 55 weight percent, 40 to 70 weight percent, 40 to 65 weight percent, 40 to 60 weight percent, 40 to 55 weight percent, 45 to 70 weight percent, 45 to 65 weight percent, 45 to 60 weight percent, 45 to 55 weight percent, for example 45 to 54 weight percent, based on the total weight of the composition.
In the present invention, the water may be deionized water, pure distilled water, or double distilled water, but is not limited thereto.
In the present invention, the water may be present in an amount of 30 to 70 weight percent, 30 to 65 weight percent, 30 to 60 weight percent, 30 to 55 weight percent, 35 to 70 weight percent, 35 to 65 weight percent, 35 to 60 weight percent, 35 to 55 weight percent, 40 to 70 weight percent, 40 to 65 weight percent, 40 to 60 weight percent, 40 to 55 weight percent, 45 to 70 weight percent, 45 to 65 weight percent, 45 to 55 weight percent, e.g., 45 to 54 weight percent, based on the total weight of the composition.
In the present invention, the above antifreeze composition may further contain an antifoaming agent.
In the present invention, the defoamer may be present in an amount of 0.005 to 0.100 wt%, 0.005 to 0.050 wt%, 0.005 to 0.010 wt%, 0.005 to 0.008 wt%, 0.004 to 0.100 wt%, 0.004 to 0.050 wt%, 0.004 to 0.010 wt%, 0.004 to 0.008 wt%, 0.003 to 0.100 wt%, 0.003 to 0.003 wt%, 0.003 to 0.010 wt%, 0.002 to 0.008 wt%, for example, 0.010 to 0.010 wt%, based on the total weight of the composition.
In the present invention, the above antifreeze composition may further contain a pH adjuster.
In the present invention, the pH adjuster may be present in an amount of 0.0005 wt% to 0.1 wt%, 0.0005 wt% to 0.01 wt%, 0.0005 wt% to 0.009 wt%, 0.0005 wt% to 0.008 wt%, 0.0005 wt% to 0.007 wt%, 0.0005 wt% to 0.006 wt%, for example, 0.0005 wt% to 0.005 wt%, based on the total weight of the composition.
In the present invention, the pH adjuster may be an amine compound.
In the present invention, the amine compound may be at least one selected from the group consisting of alkanolamines, alkylamines and cyclic amines.
In the present invention, the alkanolamine may be, but is not limited to, a monomethylolamine, a dimethanolamine, a trimethanolamine, a monoethanolamine, a diethanolamine, a triethanolamine, a monopropanolamine, a dipropanolamine, a tripropanolamine, a monoisopropanolamine, a diisopropanolamine, or a triisopropanolamine.
In the present invention, the above alkylamine may be dibutylamine, tributylamine, dicyclohexylamine, cyclohexylamine and salts thereof, piperazine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, 2-propylheptylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, isotridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, n-eicosylamine, di- (n-hexyl) amine, di- (n-heptyl) amine, di- (n-octyl) amine, di- (2-ethylhexyl) amine, di- (n-nonyl) amine, di- (n-decyl) amine, di- (2-propylheptyl) amine, di- (n-undecyl) amine, di- (n-dodecyl) amine, di- (n-tridecyl) amine, di- (isotridecyl) amine, di- (n-tetradecyl) pentadecylamine, di- (n-hexadecyl) amine, di- (n-octadecyl) amine, di- (n-eicosyl) amine, n-hexylmethylamine, n-heptylmethylamine, n-octylmethylamine, (2-ethylhexyl) methylamine, n-nonylmethylamine, n-decylmethylamine, (2-propylheptyl) methylamine, n-undecylmethylamine, N-dodecylmethylamine, n-tridecylmethylamine, isotridecylmethylamine, n-tetradecylmethylamine, n-pentadecylmethylamine, n-hexadecylmethylamine, n-heptadecylmethylamine, n-octadecylmethylamine, n-nonadecylmethylamine, n-eicosylmethylamine, di- (n-nonyl) amine, di- (n-decylmethylamine), di- (2-propylheptyl) amine, di- (n-undecylenamine, di- (n-dodecylamine, di- (n-tridecylamine, di- (isotridecylamine), di- (n-tetradecyl) amine, di- (n-pentadecylmethylamine), di- (n-hexadecylamine, di- (n-heptadecylamine), di- (n-octadecyl) amine, di- (n-nonadecylamine, di- (n-eicosylmethylamine), n-heptylmethylamine, n-octylmethylamine, (2-ethylhexyl) methylamine, n-nonylmethylamine, n-decylmethylamine, n-tridecylmethylamine, isotridecylmethylamine, n-tetradecylmethylamine, n-hexadecylmethylamine, n-heptadecylmethylamine, n-octadecylmethylamine, n-nonadecylmethylamine, n-octadecylmethylamine or n-nonadecylmethylamine.
In the present invention, the cyclic amine may be morpholine, but is not limited thereto.
In an embodiment of the invention, the amine compound may be triethanolamine.
In another embodiment of the present invention, the triethanolamine may be present in an amount of 0.0005 wt.% to 0.1 wt.%, 0.0005 wt.% to 0.01 wt.%, 0.0005 wt.% to 0.009 wt.%, 0.0005 wt.% to 0.008 wt.%, 0.0005 wt.% to 0.007 wt.%, 0.0005 wt.% to 0.006 wt.%, for example, 0.0005 wt.% to 0.005 wt.%, based on the total weight of the composition.
In the present invention, the above antifreeze composition may further comprise a metal corrosion inhibitor.
In the present invention, the metal corrosion inhibitor may be present in an amount of 0.0001 to 11.0 weight percent, 0.0001 to 10.0 weight percent, 0.0001 to 9.0 weight percent, 0.0001 to 8.0 weight percent, 0.0001 to 7.0 weight percent, 0.0001 to 6.0 weight percent, 0.0001 to 5.0 weight percent, 0.0001 to 4.0 weight percent, 0.0001 to 3.0 weight percent, 0.0001 to 2.0 weight percent, for example, 0.0001 to 1.0 weight percent, based on the total weight of the composition.
In the present invention, the metal corrosion inhibitor may be an azole such as triazole or thiadiazole, but is not limited thereto.
In the present invention, the triazole may be selected from the group consisting of triazole derivatives, benzotriazole derivatives and tolyltriazole derivatives, but is not limited thereto.
In the present invention, the triazole-based metal corrosion inhibitor includes N, N-bis (2-ethylhexyl) -4-methyl-1H-benzotriazole-1-methylamine, N-bis (2-ethylhexyl) -5-methyl-1H-benzotriazole-1-methylamine, octyl 1H-benzotriazole, di-t-butylated 1H-benzotriazole, 1H-1,2, 3-triazole, 2H-1,2, 3-triazole, 1H-1,2, 4-triazole, 4H-1,2, 4-triazole, 1- (1 ',2' -dicarboxyethyl) benzotriazole, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 1H-1,2, 3-triazole, 2H-1,2, 3-triazole, 1H-1,2, 4-triazole, 4H-1,2, 4-triazole, benzotriazole, tolyltriazole, carboxybenzotriazole, 3-amino-1, 2, 4-triazole, chlorobenzotriazole, nitrobenzotriazole, aminobenzotriazole, cyclohexyl [ 1,2-d ] triazole, 4,5,6, 7-tetrahydroxytolyltriazole, 1-hydroxybenzotriazole, ethylbenzotriazole, naphthalene triazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] tolyltriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] carboxybenzotriazole, 1- [ N, n-bis (di- (ethanol) -aminomethyl ] benzotriazole, 1- [ N, N-bis (di- (ethanol) -aminomethyl ] tolyltriazole, 1- [ N, N-bis (di- (ethanol) -aminomethyl ] carboxybenzotriazole, 1- [ N, N-bis (2-hydroxypropyl) aminomethyl ] carboxybenzotriazole, 1- [ N, N-bis (1-butyl) aminomethyl ] carboxybenzotriazole, 1- [ N, N-bis (1-octyl) aminomethyl ] carboxybenzotriazole, 1- (2 ',3' -dihydroxypropyl) benzotriazole, 1- (2 ',3' -dicarboxyethyl) benzotriazole, 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) benzotriazole, 2- (2 ' -hydroxy-4 ' -octyloxyphenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' -tert-butylphenyl) benzotriazole, 1-hydroxybenzo-6-carboxylic acid, 1-oleo-benzotriazole, 1,2, 4-amino-3, 3-amino-triazol, 1-4-3-amino-4, 5-amino-heptanol, 1-4-amino-triazol, 1-4-amino-4-2-N-3-tert-butylphenyl) benzotriazole, 3-amino-5- (4-isopropyl-phenyl) -1,2, 4-triazole, 5-amino-3-mercapto-1, 2, 4-triazole, 3-amino-5- (p-tert-butylphenyl)) -1,2, 4-triazole, 5-amino-1, 2, 4-triazole-3-carboxylic acid, 1,2, 4-triazole-3-carboxamide, 4-semicarbazide alcohol, 1,2, 4-triazole-5-and the like, but is not limited thereto.
In the present invention, the thiadiazoles may be 2, 5-dimercapto 1,3,4 thiadiazole, 2-mercapto-5-hydrocarbylthio-1, 3, 5-thiadiazole, 2-mercapto-5-hydrocarbyldithio-1, 3, 4-thiadiazole, 2, 5-bis (hydrocarbylthio) -1,3, 4-thiadiazole, 2,5, - (bis) hydrocarbyldithio-1, 3, 4-thiadiazole, or the like, but are not limited thereto.
In the present invention, the antifreeze composition may be an antifreeze composition for an internal combustion engine, an antifreeze composition for a battery, or an antifreeze composition for a fuel cell, for example, an antifreeze composition for a fuel cell.
In the present invention, the conductivity of the antifreeze composition may be 50.0uS/cm or less, for example, may be less than 50.0uS/cm. If the conductivity is above the reference value, the performance of the fuel cell stack may be degraded, with a risk of failure.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention relates to a colorant for a heat transfer fluid, which is excellent in color strength, is physically and chemically stable, and has excellent solubility in glycol antifreeze compositions, particularly in glycol antifreeze compositions, and a composition comprising the same. Therefore, the antifreeze composition of the present invention has excellent color strength, is physically and chemically stable, and has low conductivity, and thus exhibits excellent characteristics as an antifreeze for fuel cells.
Drawings
Fig. 1a is a graph of the results of confirming the structure of example 1 according to an embodiment of the present invention by nuclear magnetic resonance spectroscopy (NMR) measurement.
Fig. 1b is a graph of the result of confirming the structure of example 1 according to the embodiment of the present invention by uv-vis absorption spectroscopy.
Fig. 2a is a graph of the results of confirming the structure of example 2 according to an embodiment of the present invention by nuclear magnetic resonance spectroscopy (NMR) measurement.
Fig. 2b is a graph of the result of confirming the structure of example 2 according to the embodiment of the present invention by uv-vis absorption spectroscopy.
Fig. 3a is a graph showing an ultraviolet-visible light absorption spectrum of embodiment 1 according to an embodiment of the present invention.
Fig. 3b is a graph showing the molar absorptivity of example 1 according to an embodiment of the present invention.
Fig. 3c is a graph showing an ultraviolet-visible light absorption spectrum of example 2 according to an embodiment of the present invention.
Fig. 3d is a graph showing molar absorptivity for example 2 according to an embodiment of the present invention.
Fig. 3e is a graph showing an ultraviolet-visible light absorption spectrum of comparative example 1 according to an embodiment of the present invention.
Fig. 3f is a graph showing molar absorptivity of comparative example 1 according to the embodiment of the present invention.
Fig. 3g is a graph showing an ultraviolet-visible light absorption spectrum of comparative example 2 according to an embodiment of the present invention.
Fig. 3h is a graph showing molar absorptivity of comparative example 2 according to the embodiment of the present invention.
Best mode for carrying out the invention
An antifreeze composition comprising: 0.001 to 10.000 weight percent of a colorant having the structure of chemical formula 1 or chemical formula 2; 30 to 70 weight percent of a glycol compound; and 30 to 70 weight percent water.
Detailed Description
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are only for illustrating the present invention, and the scope of the present invention is not limited by these examples.
Preparation example 1: preparation example 1
First, a triethylenesubstituted phthalonitrile intermediate is synthesized. Specifically, 4-nitrophthalonitrile (1 equivalent (eq)) and triglyme (1.1 equivalent) were dissolved in Tetrahydrofuran (THF) and stirred under nitrogen atmosphere. After that, cesium carbonate (Cs) 2 CO 3 ) (5.5 eq.) followed by heating at 65℃for 12 hours. Then, after the reaction was allowed to return to normal temperature, 100ml of water was poured into the reaction, followed by extraction with Dichloromethane (DCM). Next, the solution was washed 3 times with water using a separating funnel and then with magnesium sulfate (MgSO 4 ) The solution was dried. After that, methylene chloride was removed by using a rotary evaporation concentrator at ordinary temperature to obtain a synthetic 4-triethylenephthalonitrile intermediate.
Then, the synthesized phthalonitrile intermediate is used to synthesize gallium-containing pigment. Specifically, 4-triethylenephthalonitrile (4 eq.) and GaCl 3 (1.5 eq.) in a pressure tube (pressure tube), 1,8-diazabicyclo (5.4.0) undec-7-ene (1, 8-diazabicyclo-7-ene, DBU) was dissolved in n-hexanol (n-hexanol) (1.5Equivalent) and heated at 180 c for 4 hours after addition. After cooling the reaction to room temperature, the supernatant n-hexanol was carefully removed. After that, hexane was added to the reaction, and the supernatant hexane was removed again. Then, the reaction was dissolved in methylene chloride, washed once with 10% hydrochloric acid, washed 3 times with water using a separating funnel, and then the solution was dried over magnesium sulfate. After that, methylene chloride was removed using a rotary evaporation concentrator. Next, a small amount of dichloromethane was added to the mixture, and then the solution was added dropwise (dropwise) to diethyl ether (diethyl ether) under stirring to recrystallize the compound to prepare a gallium-containing pigment.
Thereafter, the colorant of example 1 of the present invention was prepared by substituting polyethylene glycol on the central axis of the synthesized gallium-containing pigment. Specifically, the synthesized gallium-containing pigment (1 equivalent) and polyethylene glycol methyl ether (molecular weight 400 (i.e., PEG) 0.4K ) 10 equivalents) was dissolved, and stirred under nitrogen atmosphere. Next, potassium carbonate (K) was added to the mixture 2 CO 3 ) After stirring at 150℃for 12 hours (8 eq.) the reaction was cooled to room temperature and methylene chloride was added and the solution was washed 3 times with water using a separatory funnel. Next, water was removed using magnesium sulfate, and methylene chloride was removed using a rotary evaporator. After that, a small amount of methylene chloride was added to the mixture, and then the solution was added dropwise to diethyl ether under stirring to recrystallize the compound, to obtain the colorant of the invention of example 1 having the structure shown in the following chemical formulas 2 to 4.
Chemical formula 2-4:
preparation example 2: preparation example 2
The colorant of example 2 was prepared in a manner similar to that for the colorant of example 1 described above, except that a siliceous pigment was used instead of gallium. Specifically, dried polyethylene glycol monomethyl ether (molecular weight 400,3 equivalent) and a siliceous pigment (1 equivalent) were placed in a pressure tube, then anhydrous toluene was poured into the mixture, and sodium hydroxide (NaOH) (2.5 equivalent) dissolved in n-hexanol was added thereto, followed by stirring in a nitrogen atmosphere. Then, after the reaction was cooled to room temperature, the reaction was dissolved in methylene chloride and then washed with water 4 times using a separating funnel. After that, water was removed with magnesium sulfate, and methylene chloride was removed using a rotary evaporator. Next, a small amount of dichloromethane was added to the mixture, and then the solution was added dropwise to hexane under stirring to recrystallize the compound, to obtain the colorant of the invention example 2 having the structure shown in the following chemical formulas 2 to 5.
Chemical formula 2-5:
preparation example 3: preparation example 3
The boron-containing pigment is synthesized using phthalonitrile intermediates. Specifically, 4-triethylenephthalonitrile (1 equivalent) was put into a flask, and added to boron trichloride (BCl) at ordinary temperature under a nitrogen atmosphere 3 ) (1 eq, 1M solution in p-xylenes) and then heated at a temperature of 150℃for 1 hour. After cooling the reaction to room temperature, the reaction was extracted with dichloromethane and washed 3 times with water, then with MgSO 4 The solution was dried. After that, methylene chloride was removed using a rotary evaporation concentrator. Next, a small amount of dichloromethane was added to the mixture, and then the solution was added dropwise (dropwise) to diethyl ether (diethyl ether) under stirring to recrystallize the compound to prepare a boron-containing pigment.
Thereafter, the colorant of the present formula 1 is prepared by substituting polyethylene glycol on the central axis of the synthesized boron-containing pigment. Specifically, a synthesized boron-containing pigment (1 equivalent) and polyethylene glycol methyl ether (molecular weight 400 (i.e., PEG) 0.4K ) 1.5 equivalents) was stirred at 140℃for 10 hours under nitrogen. After cooling the reaction to room temperature, methylene chloride was added, and then the solution was washed with water 3 times using a separating funnel. Next, water was removed with magnesium sulfate and dichloromethane was removed using a rotary evaporator. Afterwards, will be lessAn amount of methylene chloride was added to the mixture, and then the solution was added dropwise to diethyl ether under stirring to recrystallize the compound, to obtain a colorant having the structure of the following chemical formula 1-2.
Chemical formula 1-2:
experimental example 1: structure validation
Experimental example 1-1: by nuclear magnetic resonance spectroscopy (NMR)
By using a magnetic resonance spectrometer (Varian-500 MHz) dissolved in deuterated chloroform (CDCl) 3 ) The measurement is performed in a solvent. The results are shown in FIG. 1a and FIG. 2a.
As shown in FIG. 1a, example 1 showed aromatic hydrogen peaks (peak) between 7.0ppm and 8.0 ppm. Also, it can be seen that a plurality of aliphatic hydrogen peaks occur between 3.0ppm and 4.2ppm, because of the molecular axial substitution of polyethylene glycol (PEG), and thus it can be confirmed that the axial substitution of polyethylene glycol (PEG) occurs.
As shown in FIG. 2a, example 2 showed unsubstituted aromatic hydrogen peaks between 7.5ppm and 8.0ppm, 8.3ppm and 9.7 ppm. Also, due to the axial substitution of polyethylene glycol, it can be seen that a plurality of aliphatic hydrogen peaks occur between 3.0ppm and 4.0ppm, which can confirm the occurrence of the axial substitution of polyethylene glycol.
Experimental examples 1-2: measurement by ultraviolet-visible absorption spectroscopy
UV-1800 spectrometer (Shimadzu corporation) was used to measure the UV-visible absorbance spectrum. The results are shown in FIG. 1b and FIG. 2b.
As shown in fig. 1b, the colorant prepared according to example 1 exhibited a bluish green color.
And, as shown in fig. 2b, the colorant prepared according to example 2 exhibited blue color.
Experimental example 2: confirming the color development
In order to confirm the color development, after the compounds having the structures shown in the following chemical formulas 3-1 to 3-5 (comparative examples 1 to 5 below) were added to the antifreeze composition mainly composed of ethylene glycol at the same concentration, respectively, the absorbance of the solution was measured using an ultraviolet-visible spectrophotometer, and the results are shown in fig. 3a to 3g and table 1.
The calculation formula:
A＝εlc
a: absorbance (absorptance), epsilon: molar absorption coefficient (molar absorption coefficient), c: molar concentration (molar concentration)
When the color development was evaluated, the absorbance was represented by excellent (very excellent) when the absorbance was > 100000, by excellent O when the absorbance was > 50000, by excellent delta when the absorbance was > 20000, and by poor X when the absorbance was 20000 or less.
Chemical formula 3-1:
chemical formula 3-2:
chemical formula 3-3:
chemical formula 3-4:
chemical formula 3-5:
TABLE 1
As shown in fig. 3a to 3h and table 1, example 1 shows bluish green, example 2 shows blue, comparative examples 1 and 2 show bluish green, comparative example 3 shows blue, comparative example 4 shows reddish yellow, and comparative example 5 shows red.
Further, by comparing the absorbance, it can be seen that the absorbance coefficient of example 1 is 58588Lmol -1 cm -1 The absorbance coefficient of example 2 is 102457Lmol -1 cm -1 The level of color development of examples 1 and 2 was excellent and very excellent, respectively.
In contrast, comparative example 1 has an absorbance of 21234Lmol -1 cm -1 The absorbance coefficient of comparative example 2 was 9032Lmol - 1 cm -1 And the absorbance coefficients of comparative examples 3 to 5 were 1000Lmol, respectively -1 cm -1 、3000Lmol -1 cm -1 3000Lmol - 1 cm -1 Hereinafter, the above-described problems are all at a poor level.
Specifically, it can be seen that examples 1 and 2 of the colorant of the present invention having a hydrophilic polymer substituent at the center of the molecular axis have significantly higher color development than comparative example 3 having no polymer substituent at both the peripheral portion and the central portion.
And, the absorbance of example 1 was about 6.52 times higher than that of comparative example 2, and the absorbance of example 2 was about 11.39 times higher than that of comparative example 2, as compared with comparative example 2 containing the polymer substituent only at the peripheral portion.
Furthermore, even if example 1 and example 2 were compared with comparative example 1 containing no polymeric substituent at the center of the molecular axis, the absorbance of example 1 was about 2.77 times higher than that of comparative example 1, and the absorbance of example 2 was about 4.84 times higher than that of comparative example 1.
Therefore, when the colorants of examples 1 and 2 according to the present invention were compared with comparative examples 1 to 5, it was confirmed that the colorant exhibited very excellent color development in the antifreeze composition mainly composed of ethylene glycol. In particular, the colorant of the present invention contains a high molecular substituent at the center of the molecular axis rather than around the molecule, and exhibits more excellent color development than the case where the substituent is contained at the peripheral portion. It was thus confirmed that the colorant of the present invention can be suitably used as a colorant having excellent color strength in an antifreeze composition.
Experimental example 3: evaluation of physicochemical stability
Thermogravimetric analysis was measured by raising the temperature to 300 ℃ in a nitrogen atmosphere at a rate of 10 ℃ per minute using a TAQ600 instrument. Acid-base stability test the change in absorbance range and absorbance intensity were measured and compared by visually observing whether the chemical in the solution of pH2 to pH12 was decomposed or not, and by uv-visible light.
When stability was evaluated, the stability was represented by goodwhen the weight change rate was 10% or less at 250 ℃ and the acid-base (alkli) stability was excellent, the stability was represented by O when the weight change rate was 20% or less at 250 ℃ and the acid-base stability was excellent, the stability was represented by delta when the weight change rate was 30% or more at 150 ℃ and the acid-base stability was excellent, and the results were represented by X in all cases, according to the results of the thermogravimetric analysis, as shown in table 2 below.
TABLE 2
Sample of Physical and chemical stability
Example 1 ◎
Example 2 ◎
As shown in Table 2 above, the results of thermogravimetric analysis of examples 1 and 2 showed that the weight change rates at 250℃were 3.4% and 8.8%, respectively, and they exhibited excellent thermal stability. In particular, examples 1 and 2 are both thermally stable up to temperatures of about 300 ℃ above which they decompose. And, acid-base stability is also very excellent. That is, it was confirmed that example 1 and example 2 were very stable thermally and chemically.
Experimental example 4: evaluation of solubility
1L of an antifreeze solution was prepared at normal temperature, and after 0.1g of the compound was added until it was completely dissolved, 0.4g was further added to confirm complete dissolution, and then 0.5g was further added and the solubility was measured by observing the solubility with naked eyes. The results are shown in Table 3 below, where the solubility in the antifreeze composition mainly composed of ethylene glycol is 1.0g/L or more and the solubility is 0.5g/L or more and O and the solubility is 0.1g/L or more and delta.
TABLE 3 Table 3
Sample of Solubility of
Example 1 ◎
Example 2 ◎
As shown in Table 3 above, example 1 and example 2 exhibited excellent solubilities of 1.1g/L and 1.2g/L, respectively, in the antifreeze compositions containing ethylene glycol as the main component. That is, it can be seen that example 1 and example 2 are better in solubility in the antifreeze solution than the conventional pigment, and therefore it is confirmed that the excellent solubility of the colorant of the invention in the antifreeze solution composition can stably and uniformly develop color in the antifreeze solution composition.
Experimental example 5: evaluation of Electrical insulation
By using TCX-90 3 The instrument measures the antifreeze composition (about 0.001 mM) of the compound to measure conductivity. When the electrical insulation property was evaluated, the antifreeze composition was represented by excellent when the electrical conductivity was 3.0uS/cm or less, O when the electrical conductivity was 3.0uS/cm to 10.0uS/cm, delta when the electrical conductivity was 10.0uS/cm to 20.0uS/cm, and X when the electrical conductivity was not less than, and the results were shown in Table 4 below.
TABLE 4 Table 4
Sample of Electrical insulation property
Colorant 1 ◎
Colorant 2 ◎
As shown in Table 4 above, it can be seen that the antifreeze compositions of the embodiment 1 and 2 each have extremely low conductivity of 3uS/cm or less. That is, it was confirmed that the antifreeze composition containing the colorant of the invention was excellent in electrical insulation.
Experimental example 6: evaluation of fouling properties on ion exchange resins
Contamination of ion exchange resins is a measure of the degree of contamination of ion exchange resins that is used to remove ions that elute from the fuel cell stack and the radiator while increasing conductivity. Specifically, after passing an antifreeze composition (about 0.001 mM) containing a compound through an ion exchange resin, the conductivity and absorbance intensity of the solution before and after passing are compared. The results of the determination of good when the conductivity and absorbance intensity of the solution before and after passing were equal to or higher than 99% and the determination of poor in other cases are shown in table 5.
TABLE 5
Sample of Contamination of ion exchange resins
Example 1 Good quality
Example 2 Good quality
As shown in Table 5 above, it was confirmed that neither example 1 nor example 2 contaminated the ion exchange resin.
Industrial applicability
The present invention relates to a colorant for a heat transfer fluid and a composition comprising the same.

Claims (14)

1. An antifreeze composition, which is characterized in that,
comprising:
0.001 to 10.000 weight percent of a colorant having the structure of chemical formula 2-4 or chemical formula 2-5;
30 to 70 weight percent of a glycol compound; and
30 to 70 weight percent water, wherein:
chemical formula 2-4:
chemical formula 2-5:
2. the antifreeze composition of claim 1, wherein the colorant has a solubility of 1g/L or more in the antifreeze composition.
3. The antifreeze composition according to claim 1, wherein the colorant has a weight loss rate of 10% or less at a temperature of 250 ℃ or less.
4. The antifreeze composition of claim 1, wherein said glycol compound is at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, polyalkylene glycol, and glycol ethers.
5. The antifreeze composition of claim 1, wherein said antifreeze composition further comprises from 0.005 to 0.100 weight percent of an antifoaming agent, based on the total weight of the composition.
6. The antifreeze composition of claim 1, wherein said antifreeze composition further comprises from 0.0005 weight percent to 0.1 weight percent of a pH adjuster, based on the total weight of the composition.
7. The antifreeze composition of claim 6, wherein said pH adjuster is an amine compound.
8. The antifreeze composition according to claim 7, wherein the amine compound is at least one selected from the group consisting of alkanolamines, alkylamines, and cyclic amines.
9. The antifreeze composition of claim 7, wherein said amine compound is triethanolamine.
10. The antifreeze composition of claim 1, wherein said antifreeze composition further comprises a metal corrosion inhibitor.
11. The antifreeze composition of claim 10, wherein said metal corrosion inhibitor is an azole.
12. The antifreeze composition according to claim 1, wherein the antifreeze composition is an antifreeze composition for an internal combustion engine or an antifreeze composition for a battery.
13. The antifreeze composition of claim 12, wherein said cell is a fuel cell.
14. The antifreeze composition of claim 1, wherein said antifreeze composition has a conductivity of 50.0uS/cm or less.
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US20220363697A1 (en) 2022-11-17
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